Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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PRODUCTION OF RENEWABLE FUELS AND INTERMEDIATES
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority of U.S.
Provisional Patent
Application No. 62/563,577 filed September 26, 2017, which is hereby
incorporated by
reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to the production of hydrocarbons from
renewable plant
and animal-based resources.
BACKGROUND
[0003] Biofuels that can be produced from renewable domestic resources
offer an
alternative to petroleum-based fuels. In order to encourage the production and
consumption
of biofuels in the United States, regulatory agencies have taken steps to
mandate and
incentivize increased production of fuels from renewable sources. California's
Low Carbon
Fuel Standard Program (LCFS) requires producers of petroleum-based fuels to
reduce the
carbon intensity of their products, beginning with a quarter of a percent in
2011, and
culminating in a 10 percent total reduction in 2020. Petroleum importers,
refiners, and
wholesalers can either develop their own low carbon fuel products, or buy LCFS
Credits
from other companies that develop and sell low carbon alternative fuels.
[0004] Likewise, the United States Congress created the Renewable
Fuel Standard
(RFS) program to reduce greenhouse gas emissions and expand the nation's
renewable fuels
sector while reducing reliance on imported oil. This program was authorized
under the
Energy Policy Act of 2005, and the program was further expanded under the
Energy
Independence and Security Act of 2007. Being a national policy, the RFS
program requires
the replacement or reduction of a petroleum-based transportation fuel, heating
oil, or jet fuel
with a certain volume of renewable fuel. The four renewable fuel categories
under the RFS
program include biomass-based diesel, cellulosic biofuel, advanced biofuel,
and total
renewable fuel.
[0005] Current commercial production methods include esterification
of triglycerides,
fats, and fatty acids, transesterification of fatty esters, fermentation of
sugar, catalytic
upgrading of sugars, and biogas- and biomass-to-liquids methods. These methods
have been
primarily focused on the production of ethanol and biodiesel, and have not
been very
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successful for producing large quantities of non-oxygenated renewable fuels.
However,
production of renewable hydrocarbons will help producers meet increasing
environmental
regulations and offer an attractive alternative for consumers that are
interested in
environmentally-friendly fuel alternatives which are replacements for non-
renewable
hydrocarbon components. Thus, there is a need in the industry for commercially
feasible
methods for the production of fuels from renewable sources.
SUMMARY
[0006] The present disclosure provides a method for producing a
renewable
hydrocarbon product from renewable fat and renewable oil feed stocks. The
renewable fat
and oil feed stocks are converted into a renewable paraffinic intermediate,
which is then used
to produce a renewable hydrocarbon product. The renewable hydrocarbon product
may
include a number of different fractions, including gasoline, diesel, and
aviation fuel.
Conditions for the production of the renewable hydrocarbon product may be
adjusted to favor
the production one fraction over others. For example, production conditions
may be adjusted
to favor the production of a renewable hydrocarbon product having a gasoline
fraction as the
major or primary constituent.
[0007] Some aspects of the present disclosure are directed to process
for producing a
renewable hydrocarbon fuel product comprising the steps of hydrotreating a
renewable feed
stock to produce a renewable paraffinic intermediate, optionally blending at
least 1% by
volume of the renewable paraffinic intermediate with an additional feed to
produce a blend,
and reacting the renewable paraffinic intermediate or the blend containing at
least 1% by
volume of the renewable paraffinic intermediate in a reaction zone under
conditions sufficient
to crack at least a portion of the renewable paraffinic intermediate or the
blend to produce a
renewable hydrocarbon fuel product. In some aspects, the reacting step
comprises fluid
catalytic cracking.
[0008] Some embodiments of the disclosure are directed to a renewable
hydrocarbon
fuel product having a "C isotopic ratio characteristic of a blend of petroleum
and at least 1%
by volume non-petroleum origin, and comprising less than about 5% coke. Some
embodiments are directed to a blended renewable hydrocarbon product comprising
a
renewable hydrocarbon fuel product having a "C isotopic ratio characteristic
of a blend of
petroleum and at least 1% by volume non-petroleum origin, and comprising less
than about
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5% coke, and a second component comprising at least one of one or more
petroleum fuel
products and one or more renewable fuels.
[0009] Some aspects of the present disclosure are directed to a
process for producing a
renewable hydrocarbon fuel product comprising the steps of hydrotreating a
renewable feed
stock to produce a renewable paraffinic intermediate, blending at least 1% by
volume of the
renewable paraffinic intermediate with an additional feed to produce a blend,
distilling the
blend to produce at least one distilled fraction having at least 1% by volume
of the renewable
paraffinic intermediate, and reacting the at least one distilled fraction in a
reaction zone under
conditions sufficient to crack at least a portion of the at least one
distilled fraction to produce
a renewable hydrocarbon fuel product. In some aspects, the additional feed is
a petroleum-
based material. Examples of petroleum-based materials include but are not
limited to crude
oil and gas oil.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a flow diagram depicting the steps involved in the
production of a
renewable hydrocarbon product, e.g., renewable gasoline.
[0011] FIG. 2 is a flow diagram depicting steps involved in the
production of a
renewable hydrocarbon product, and potential uses of the renewable hydrocarbon
product,
including sales and further processing.
DETAILED DESCRIPTION
[0012] Various features and advantageous details are explained more fully
with
reference to the non-limiting embodiments that are illustrated in the
accompanying drawing
and detailed in the following description. It should be understood, however,
that the detailed
description and the specific examples, while indicating embodiments of the
invention, are
given by way of illustration only, and not by way of limitation. Various
substitutions,
modifications, additions, and/or rearrangements will become apparent to those
of ordinary
skill in the art from this disclosure.
[0013] In the following description, numerous specific details are
provided to provide
a thorough understanding of the disclosed embodiments. One of ordinary skill
in the relevant
art will recognize, however, that the invention may be practiced without one
or more of the
specific details, or with other methods, components, materials, and so forth.
In other
instances, well-known structures, materials, or operations are not shown or
described in detail
to avoid obscuring aspects of the invention.
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[0014]
The present disclosure provides a method for producing a renewable
hydrocarbon fuel product from renewable fat and renewable oil feed stocks. The
renewable
fat and oil feed stocks are initially converted into a renewable paraffinic
intermediate stream
by a hydrotreating process. The renewable feed stock and/or renewable
paraffinic
intermediate can optionally be blended with other hydrocarbon streams,
including crude oil,
gas oil, fuel oils, diesel, and other petroleum distillates.
The renewable paraffinic
intermediate or blended intermediate is then processed in a cracking unit, for
example, a fluid
catalytic cracking unit, to produce the renewable hydrocarbon fuel product.
The renewable
fuel product may include a number of fractions, including, but not limited to,
a fuel gas,
ethylene, propylene, butylene, LPG, naphtha, gasoline, diesel, cycle oils,
light cycle oil, and
cat unit bottoms (slurry/decant oil). The renewable hydrocarbon fuel product
may be further
refined, for example, separated into constituent fractions and/or blended with
other
hydrocarbons, such as petroleum-based hydrocarbons or one or more renewable
fuels, for
example, ethanol, to produce a renewable hydrocarbon blended fuel product. The
production
process is flexible; the cracking conditions may be altered in order to favor
the selective
production of one or more fractions.
[0015]
Generally, the renewable fats and renewable oils serving as original feed
stocks
are predominantly non-petroleum fats and oils. The renewable fats and
renewable oils may
originate from plant and animal sources. The fats and oils may include used
cooking oil,
recycled cooking oil, waste cooking oil, used vegetable oil, recycled
vegetable oil, waste
vegetable oil, rendered oils, animal fats, tallow, pork fat, chicken fat, fish
oils, yellow grease,
poultry fat, algal oils, algae-derived oils, soy oil, palm oil, palm fatty
acids, plant-derived oils
such as corn oil, canola oil, jatropha oil, olive oil, fatty acids, and seed
oils, and the like. In
one embodiment, the feed stock comprises at least 10% used cooking oil. In
embodiments,
the used stock comprises at least 10% used corn oil. In further embodiments,
the feed stock
comprises at least 10% used cooking oil and at least 10% used corn oil. The
renewable fats
and oils may be used alone, or may be used in combination. Low-quality grade
fats and oils
are customarily used for, or in some instances recycled into, animal feed
stocks, personal
care, and household products such as soap and detergent. The present
disclosure provides a
method for employing new and/or recycled renewable fats and oils as feed
stocks for the
production of renewable fuels such as gasoline, diesel, and aviation fuel, and
chemical
intermediates such as ethylene, propylene and butylene.
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[0016] In some aspects, a process for producing a renewable
hydrocarbon fuel product
from a renewable feed stock is provided. A renewable hydrocarbon fuel product
includes a
renewable hydrocarbon that can be further refined and a renewable hydrocarbon
blend stock
that may be further processed to produce a sellable product. The process
includes
hydrotreating (and optionally isomerizing, dewaxing, and/or hydrocracking) the
renewable
feed stock to produce a renewable paraffinic intermediate, optionally blending
the renewable
paraffinic intermediate with an additional feed, and reacting at least a
portion of the
renewable paraffinic intermediate or blend in a reaction zone under conditions
sufficient to
crack at least a portion of the renewable paraffinic intermediate or blend to
produce a product
stream comprising a renewable or partially-renewable hydrocarbon fuel product.
In some
aspects, reacting at least a portion of the renewable paraffinic intermediate
or blend in a
reaction zone under conditions sufficient to crack at least a portion of the
renewable
paraffinic intermediate or blend comprises fluid catalytic cracking. The
additional feed may
comprise other hydrocarbon streams, such as a conventional petroleum-based
intermediate to
be cracked, including gas oil, distillates, atmospheric tower bottoms, cycle
oils, and/or crude
oil.
[0017] In some aspects, hydrotreating the renewable feed stock
involves contacting the
renewable feed stock with a catalyst in the presence of hydrogen at elevated
temperature to
produce a renewable paraffinic intermediate, which may be further hydro-
processed or
isomerized. Hydrotreating is understood to broadly refer to processes that
treat a feed stock
with hydrogen, and reactions that occur during hydrotreating include
hydrodeoxygenation,
hydrodesulfurization, hydrodenitrification, and saturation of olefins. The
renewable feed
stocks may comprise triglycerides and fatty acids (typically with chain
lengths of C12-C24),
anhydrides, esters, and combinations thereof. Esters may include mono-alcohol
esters and
polyol esters, such as triglycerides. The hydrotreating process may be a hydro-
deoxygenation
and hydrogenation process in which esters are cleaved, oxygenated compounds
including
acids and alcohols are reduced to the corresponding paraffins, and double
bonds are
saturated. Glycerin may be liberated during ester cleavage and
hydrodeoxygenated to form
propane. The renewable paraffinic intermediate may include, in addition to
propane, butane.
More specifically, some butane, for example, n-butane, is produced during the
hydrotreating
process and may be separated from the renewable paraffinic intermediate and
fed to an
isomerization unit where it is converted to isobutane. In some embodiments,
double bonds
are reduced during hydrotreating. In some aspects, the hydrotreating process
reduces the
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level of contaminants, including, but not limited to, Na, Ca, Mg, K, P, S, N,
Cl, Si, Mg, K,
Al, and oxygenated compounds. The renewable feed stock may be blended with a
petroleum
feed prior to or during the hydrotreating step. The hydrotreating process may
be performed at
a pressure ranging from about 100 psig to about 3,400 psig, preferably at a
pressure ranging
from about 400 psig to about 1,800 psig. In some aspects, the hydrotreating
process is
carried out at a temperature ranging from about 250 C to about 430 C.
Catalysts for the
hydrotreating process include, but are not limited to, Ni-Mo and Co-Mo
catalysts. In some
aspects, the hydrotreating process liquid hourly space velocity (LHSV) may
range from about
0 to about 2.0 (hr-1). A preferred hydrotreating reaction system includes at
least one reactor,
each of which has at least one or more catalyst beds. In some embodiments, the
hydrotreating process is performed in a hydrotreating reactor having at least
three beds.
[0018] In some aspects, the renewable feed stock is pre-treated prior
to the
hydrotreating step. Pre-treating may include one or more of a degumming step,
a water-wash
step, a demetallation step, a bleaching step, an ion-exchange step, a full (or
partial)
hydrogenation step, an acid gas removal step, and a water removal step.
Degumming
involves removal of gums and phosphorus compounds, such as phospholipids.
Demetallation
involves removal of metals, some of which may be harmful to the hydrotreating
catalyst. In
some aspects, the demetallation process produces a feed stock having a metal
contaminant
level of below 18 ppm. Acid gas removal includes removal of gases such as CO2
and H25.
Each of the pre-treating and hydrotreating steps may involve the use of one or
more catalysts.
The renewable feed stock may be blended with a petroleum feed prior to or
during the pre-
treating step.
[0019] The renewable paraffinic intermediate may be blended with a
petroleum-based
intermediate in an amount greater than 0% to less than 99% by volume of
renewable
paraffinic intermediate. These amounts may also range from greater than 0% to
less than
80%, greater than 0% to less than 70%, greater than 0% to less than 60%,
greater than 0% to
less than 50%, greater than 0% to less than 40%, greater than 0% to less than
30%, greater
than 0% to less than 20%, and greater than 0% to less than 10%, in each case
by volume of
renewable paraffinic intermediate. In some aspects, the renewable paraffinic
intermediate is
further reacted in a cracking unit essentially in the absence of a sulfur
removal pre-treatment
step prior to entry of the renewable paraffinic intermediate into the cracking
unit.
[0020] In some embodiments, the renewable paraffinic intermediate or
blend has a
boiling point range from 180 C to 400 C; if co-processed with petroleum
based feed stocks,
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the boiling point range may be increased beyond these levels. In some aspects,
the renewable
paraffinic intermediate, derived from triglycerides and fatty acids, and
absent any co-
processing, comprises greater than 90% paraffin compounds, and is
substantially free of
aromatic compounds; the renewable paraffinic intermediate may contain aromatic
or
naphthenic compounds if co-processed or blended with petroleum-based feed
stocks or other
known aromatic or naphthenic mixtures. Petroleum and other renewable feed
stocks may be
blended or added, either before, during or after, the pre-treatment and/or
hydrotreating step.
The renewable paraffinic intermediate or blend produced by the methods
disclosed herein
may have a lower cloud point and/or freezing point than a conventional,
petroleum-based
intermediate counterpart. In some aspects, the freezing point of the renewable
paraffinic
intermediate or blend may range from -50 C to 50 C. In some aspects, the
density of the
renewable paraffinic intermediate or blend may range from 0.7 to 0.92 grams
per cubic
centimeter. The renewable paraffinic intermediate or blend may comprise 50 ppm
or less,
preferably 10 ppm or less, of Na, Ca, Mg, K, P, Mg, K, or other contaminants,
providing no
co-processing. In some embodiments, the renewable paraffinic intermediate or
blend has an
oxygen content of less than 11%. In particular instances, the renewable
paraffinic
intermediate has an oxygen content of less than 1%. In some aspects, the
renewable
paraffinic intermediate or blend is substantially free of fatty acids and/or
fatty esters. The
renewable paraffinic intermediate or blend may contain propane, resulting from
hydrogenation of glycerin. In some embodiments, at least a portion of any
propane resulting
from triglyceride hydrotreating (i.e., hydrogenation of glycerin to propane),
is separated from
the renewable paraffinic intermediate, and is fed to a cracking unit where it
is cracked into
lighter products. In some aspects, the renewable paraffinic intermediate or
blend has a "C
isotopic ratio characteristic of non-petroleum origin for the paraffinic
intermediate or, in the
case of a blend, a "C isotopic ratio characteristic of a blend of petroleum
and non-petroleum
origins according to the percent by volume of each component. In some aspects,
the
renewable paraffinic intermediate or blend comprises at least 80% C8-C20
hydrocarbons,
preferably at least 90% C8-C20 hydrocarbons, and more preferably at least 95%
C8-C20
hydrocarbons. In some embodiments, the renewable paraffinic intermediate or
blend is
substantially free of aromatics and sulfur. In some aspects, the renewable
paraffinic
intermediate or blend has a pour point in the range of -18 C to 50 C. In
some embodiments,
the renewable paraffinic intermediate or blend has a flash point greater than
20 C. In further
embodiments, the renewable paraffinic intermediate or blend has a California
Air Resource
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Board Certified LCFS carbon intensity value less than 55, as defined at
http s ://www. arb . ca.gov/fuel s/lcfs/fuelp athway s/p athwaytable. htm .
[0021] Optionally, the renewable intermediate stream may be further
processed to
reduce the pour point of the intermediate prior to routing to the cracking
unit. This may
include commonly known refining steps such as dewaxing, isomerization, and/or
hydrocracking. Alternatively the renewable intermediate may be blended with
other
petroleum or renewable based materials in order to lower the pour point of the
mixture prior
to routing to an FCC unit. Lowering the pour point to the range of -18 C to
50 C will aid in
reducing gelling or solidification that may otherwise occur prior to cracking
in an FCC unit.
[0022] In some aspects, conditions sufficient to crack at least a portion
of the
renewable paraffinic intermediate or blend comprise reacting the intermediate
or blend in a
cracking unit, such as a fluid catalytic cracking unit or hydrocracking unit.
In some aspects,
conditions sufficient to crack at least a portion of the renewable paraffinic
intermediate or
blend comprise contacting the renewable paraffinic intermediate or blend with
a fluid
catalytic cracking catalyst in a fluid catalytic cracking reactor at elevated
temperature and
pressure. In some aspects, the temperature may range from 400 C to 800 C. In
other
embodiments, the temperature may range from about 475 C to about 600 C,
preferably
from about 490 C to about 600 C, and more preferably from about 500 C to
about 550 C.
In some embodiments, the pressure may range from greater than 0 to 80 psig. In
other
embodiments, the pressure may range from about 5 to about 80 psig, preferably
from about
10 to about 55 psig. The catalyst may be an aluminosilicate catalyst, such as
a zeolite
catalyst, or other catalyst commonly used in a fluidized cracking reactor. In
some
embodiments, a catalyst to oil feed ratio may range from about 2:1 to about
20:1 by weight,
preferably from about 4:1 to about 10:1. In some aspects, a reactor stripping
steam/catalyst
ratio may range from about 0.5 to about 6 pounds steam/1,000 pounds catalyst,
preferably
about 2 pounds steam/1,000 pounds catalyst. In some embodiments, the
composition has a
catalyst-to-feed stock ratio ranging from 2:1 to 10:1 by weight, and the
renewable paraffinic
intermediate or blend fed to the reactor has an oxygen content of less than
11% and is
substantially free of fatty acids and/or fatty esters. In some embodiments,
the amount of the
composition is greater than 100 kilograms.
[0023] In a specific embodiment, cracking of the renewable paraffinic
intermediate is
performed in a fluidized bed reactor with a catalyst made up of finely divided
or particulate
solid material. In a particular aspect, cracking of the renewable paraffinic
intermediate is
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performed in a fluid catalytic cracking unit (FCC). In a fluid catalytic
cracking unit, the
catalyst is suspended in a reaction zone by passing liquid, gas, and/or vapor
through the
catalyst particles. The renewable paraffinic intermediate comes into contact
with the
fluidized catalyst particles which catalyze the cracking reaction. The
cracking conditions
(temperature, pressure, catalyst to oil ratio) may be adjusted such that the
cracking process
(yield, conversion, selectivity, etc.) meets the requirements of production.
During the
cracking process, coke (solid carbonaceous material) becomes deposited on the
catalyst
particles. The catalyst particles are partially deactivated by the deposition
of coke and may
be transferred to a stripping zone for removing adsorbed hydrocarbons and
gases from
catalyst. The stripped catalyst particles are transferred to a regeneration
zone for oxidative
coke removal by using air or oxygen-enriched air. The regenerated catalyst
particles may
then be reintroduced into the reaction zone for continued cracking catalysis.
The cracking
process may involve cyclically repeating the cracking and catalyst
regeneration steps to
continuously produce the renewable hydrocarbon fuel product. In a specific
embodiment,
the process is run continuously for at least 1 month, preferably for at least
6 months. In
various embodiments, the reacting or cracking step produces renewable
hydrocarbon fuel
product in an amount of at least 100 liters per day.
[0024] Referring now to Figure 1, a flow diagram is depicted with an
embodiment of
the steps involved in the production of a renewable hydrocarbon fuel product,
which may be
further refined or further blended to produce a renewable blended product or
partially
renewable blended product, for example, renewable gasoline. In this
embodiment, a
renewable animal or plant-based feed stock, such as fat, undergoes
hydrotreatment, i.e.,
cleavage of triglycerides and decarboxylation of fatty acids under reductive
hydrogenation
conditions. Additional components added at the hydrotreating stage may include
diesel or gas
oil. The feed stock may optionally undergo pre-treatment prior to
hydrotreatment to improve
the hydrotreatment process. The intermediate from hydrotreating may optionally
undergo
pre-treatment, or cracker unit feed hydrotreating, including blending with
other hydrocarbon
components, such as gas oil or ATB's (atmospheric tower bottoms). The
resulting
intermediate is transported to a fluid catalytic cracking unit and reacted
with a cracking
catalyst under appropriate cracking conditions to yield a renewable
hydrocarbon fuel product
with properties similar to petroleum-derived components.
[0025] Some aspects of the disclosure are directed towards a
hydrocarbon fuel product
in industrially relevant amounts by cracking, preferably fluid catalytic
cracking (FCC), of a
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renewable intermediate feed stock as described herein, wherein the renewable
intermediate
feed stock can be processed in the cracking unit essentially by itself, or co-
processed as a
blend with an additional feed stock stream. In such cases, the product from
the cracking unit
is a renewable hydrocarbon fuel product produced in an industrially relevant
amount by the
process as described herein. By industrially relevant amounts is meant amounts
that enter the
consumer market rather than laboratory scale amounts. In one example,
industrially relevant
amounts are produced continuously at greater than 100 liters renewable
hydrocarbon fuel
product per day for a time period of at least one month.
[0026] In some aspects, the renewable hydrocarbon fuel product has a
"C isotopic
ratio characteristic of a blend of petroleum and non-petroleum origins with at
least 1% by
volume of non-petroleum origins, i.e., derived from the renewable intermediate
feed stock.
In some aspects of the invention, the renewable hydrocarbon fuel product
comprises less than
about 5% coke. In some embodiments, the renewable hydrocarbon fuel product has
a boiling
point ranging from 180 C to 400 C. In some aspects, the renewable
hydrocarbon fuel
product has a specific gravity between about 0.55 and about 0.92, preferably
between about
0.72 and about 0.92. In some embodiments, the renewable hydrocarbon fuel
product has a
cloud point between about -20 C and about 50 C. In some aspects, the
renewable
hydrocarbon fuel product has an isoparaffin to normal paraffin ratio of about
0.0 to about 9Ø
An isoparaffin to normal paraffin ratio of 0.0 corresponds to a renewable
hydrocarbon fuel
product having essentially no isoparaffin. The renewable hydrocarbon fuel
product may have
less than 20 ppm of Na, Ca, Mg, K, P, Mg, K, or other contaminants. In some
aspects, the
renewable hydrocarbon fuel product has less than 10 ppm of Na, Ca, Mg, K, P,
Mg, K, or
other contaminants. In some aspects, the renewable hydrocarbon fuel product
may have a
sulfur content less than about 0.2 weight % of a total weight of the renewable
hydrocarbon
fuel product. In some aspects, the freezing point of the renewable hydrocarbon
fuel product
may range from -50 C to 50 C. In particular aspects, the freezing point of
the renewable
hydrocarbon fuel product may range from -20 C to 40 C.
[0027] The renewable hydrocarbon fuel product may have a lower cloud
point and/or
freezing point than a conventional, petroleum-based blend stock counterpart.
In some
aspects, the renewable hydrocarbon fuel product may be used as a blend stock
and combined
with one or more petroleum fuel products and/or renewable fuels. Upon blending
with other
products, the blending of materials will change the properties of the
renewable hydrocarbon
fuel product or blend stock. Examples of renewable fuels include but are not
limited ethanol,
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propanol, and butanol. Petroleum-based streams include, but are not limited to
gasoline,
diesel, aviation fuel, or other hydrocarbon streams obtained by refining of
petroleum. The
amount of petroleum-based stream blended with the renewable hydrocarbon fuel
product may
be greater than 0% to less than 99% by volume of renewable hydrocarbon fuel
product.
These amounts may also range from greater than 0% to less than 80%, greater
than 0% to less
than 70%, greater than 0% to less than 60%, greater than 0% to less than 50%,
greater than
0% to less than 40%, greater than 0% to less than 30%, greater than 0% to less
than 20%, and
greater than 0% to less than 10%, in each case by volume of renewable
hydrocarbon fuel
product. In particular aspects, the renewable hydrocarbon fuel product is
blended to produce
a product selected from gasoline, aviation fuel, light cycle oil, and diesel.
The renewable
hydrocarbon fuel product or the blended product used to produce gasoline or
aviation fuel
may have an octane rating ranging from 40 to 110, preferably from 50 to 98. In
particular
aspects, the octane rating may range from 80 to 95. The octane rating is
defined as the
number average of research octane number (RON) and motor octane number (MON).
Some
aspects of the disclosure are directed to gasoline comprising at least 1% by
volume of the
renewable hydrocarbon fuel product produced in an industrially relevant
amount. Some
aspects of the disclosure are directed to aviation fuel comprising at least 1%
by volume of the
renewable hydrocarbon fuel product produced in an industrially relevant
amount. Some
aspects of the disclosure are directed to light cycle oil comprising at least
1% by volume of
the renewable hydrocarbon fuel product produced in an industrially relevant
amount.
[0028] The renewable hydrocarbon fuel product may be sold or further
processed.
Examples of further processing include blending, hydroprocessing, or
alkylating at least a
portion of the renewable hydrocarbon fuel product. The renewable hydrocarbon
fuel product
may be separated into two or more constituent streams. Constituent streams
include but are
not limited to a fuel gas stream, an ethylene stream, a propylene stream, a
butylene stream, an
LPG stream, a naphtha stream , an olefin stream, a diesel stream, a gasoline
stream, a light
cycle oil stream, an aviation fuel stream, a cat unit bottoms (slurry/decant
oil) stream, and
other hydrocarbon streams. In some aspects, a constituent stream may be
further processed.
In specific embodiments, an olefinic constituent stream may be sent to an
alkylation unit
and/or a dimersol unit for further processing. In addition, olefins from the
constituent
streams may be further separated and recovered for use in renewable plastics
and
petrochemicals.
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[0029] In various embodiments, the renewable paraffinic intermediate
described
herein, or the renewable hydrocarbon fuel product described herein, or both,
may be used in
existing infrastructure for petroleum-based equivalents without the need for
modification of
existing physical units including pipelines, holding units, and reactors.
[0030] A "glyceride" is an ester of glycerol and at least carboxylic acid.
Glycerides
include mono-, di-, and triglycerides. The terms "a" and "an" are defined as
one or more
unless this disclosure explicitly requires otherwise. The term "substantially"
is defined as
being largely but not necessarily wholly what is specified (and include wholly
what is
specified) as understood by one of ordinary skill in the art. In any disclosed
embodiment, the
term "substantially" may be substituted with "within [a percentage] of' what
is specified,
where the percentage includes .1, 1, 5, and 10 percent. The terms "comprise"
(and any form
of comprise, such as "comprises" and "comprising"), "have" (and any form of
have, such as
"has" and "having"), "include" (and any form of include, such as "includes"
and "including")
and "contain" (and any form of contain, such as "contains" and "containing")
are open-ended
linking verbs. As a result, a catalyst composition that "comprises," "has,"
"includes" or
"contains" one or more elements possesses those one or more elements, but is
not limited to
possessing only those one or more elements. Likewise, an element of a system
or
composition that "comprises," "has," "includes" or "contains" one or more
features possesses
those one or more features, but is not limited to possessing only those one or
more features.
[0031] The feature or features of one embodiment may be applied to other
embodiments, even though not described or illustrated, unless expressly
prohibited by this
disclosure or the nature of the embodiments. Any embodiment of any of the
disclosed
composition, system, or process can consist of or consist essentially of,
rather than
comprise/include/contain/have, any of the described elements and/or features
and/or steps.
Thus, in any of the claims, the term "consisting of' or "consisting
essentially of' can be
substituted for any of the open-ended linking verbs recited above, in order to
change the
scope of a given claim from what it would otherwise be using the open-ended
linking verb.
Details associated with the embodiments described above and others are
presented below.
EXAMPLES
Example 1- Renewable intermediate feed stock produced by hydrotreating:
[0032] In a hydrotreating process, 100 bbl of a renewable
triglyceride react with 1,800
scf/bbl of hydrogen to produce 106 bbl of a mixture of hydrocarbons. In an
exemplary
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hydrotreating process, 100 bbl of a renewable triglyceride will produce 106
bbl of
hydrocarbons with a specific gravity of approximately 0.78 and small amounts
of light gases.
The hydrotreating process produces more hydrocarbons per unit volume of
starting
triglyceride, and does not require an additional methanol source. Oxygen-
containing
.. compounds are largely converted into the corresponding hydrocarbons, water,
CO, and CO2.
Example 2- Characterization and Comparison of Renewable FCC Products:
[0033]
Cracking a petroleum-based feed in an FCC yields a higher amount of coke as
compared with a renewable intermediate feed. The coke produced (wt%) during
cracking of
a petroleum-based feed is greater than 6 wt%. By contrast, cracking a
renewable
intermediate feed yields approximately 2.2 wt% coke. As a result of the
reduced coke
production, the renewable intermediate can be fed to the cracking unit at a
higher rate, the
cracking unit can be operated at more severe reaction conditions, and the
catalyst to oil ratio
can be increased, which would result in increased product conversion.
Table 1 Petroleum-Based vs. Renewable Intermediate FCC Yields
Petroleum-Based FCC Yields
Renewable Intermediate FCC Yields
Liquid Volume % Liquid Volume %
LPG 33.4 LPG 39.2
Gasoline 47.1 Gasoline 40.4
LCO 21.8 LCO 35.4
Slurry 6.0 Slurry 1.4
Coke, wt% 6.3 Coke, wt% 2.2
Total 108.3 Total 116.4
[0034]
Implementation of the renewable hydrocarbon production methods disclosed
herein presents an economically viable, environmentally friendly approach to
supplement
current petroleum-based fuel production methods.
The methods disclosed herein
demonstrate desirable process conditions, and allow for the acquisition of
valuable
environmental regulation credits to use and sell.
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[0035] The claims are not to be interpreted as including means-plus- or
step-plus-
function limitations, unless such a limitation is explicitly recited in a
given claim using the
phrase(s) "means for" or "step for," respectively.
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